JPS6210210B2 - - Google Patents
Info
- Publication number
- JPS6210210B2 JPS6210210B2 JP52060767A JP6076777A JPS6210210B2 JP S6210210 B2 JPS6210210 B2 JP S6210210B2 JP 52060767 A JP52060767 A JP 52060767A JP 6076777 A JP6076777 A JP 6076777A JP S6210210 B2 JPS6210210 B2 JP S6210210B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- methyl
- group
- general formula
- tbco
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- -1 polyene compound Chemical class 0.000 claims description 23
- NJQJGRGGIUNVAB-UHFFFAOYSA-N 2,4,4,6-tetrabromocyclohexa-2,5-dien-1-one Chemical compound BrC1=CC(Br)(Br)C=C(Br)C1=O NJQJGRGGIUNVAB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZRDGLFJNQLTOLC-UHFFFAOYSA-N COC(C=CCCC=CCCC=CCC)=O Chemical group COC(C=CCCC=CCCC=CCC)=O ZRDGLFJNQLTOLC-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229930014550 juvenile hormone Natural products 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 150000003633 juvenile hormone derivatives Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NQEKGMWPZUWNSN-FNFKDMCFSA-N methyl (2e,6e,10e)-3,7,11,15-tetramethylhexadeca-2,6,10,14-tetraenoate Chemical compound COC(=O)\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C NQEKGMWPZUWNSN-FNFKDMCFSA-N 0.000 description 1
- IYSZVOVZPVKXIJ-UHFFFAOYSA-N methyl dodeca-2,6-dienoate Chemical compound CCCCCC=CCCC=CC(=O)OC IYSZVOVZPVKXIJ-UHFFFAOYSA-N 0.000 description 1
- QDRAZQUDJWLHBL-UHFFFAOYSA-N methyl trideca-2,6-dienoate Chemical compound COC(C=CCCC=CCCCCCC)=O QDRAZQUDJWLHBL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は下記一般式（）
〔式（）中R1およびR2は同一または異なる低級
アルキル基を表わし、R3はシアノ基またはアル
コキシカルボニル基によつて置換されている飽和
または不飽和の脂肪族炭化水素基を表わし、数字
はそれが付されている炭素原子の位置を表わす〕
で示されるポリエン化合物に対し、３位の炭素に
臭素原子を、２位の炭素に水酸基またはメトキシ
基を付加した形の臭素化物の製造方法に関する。[Detailed Description of the Invention] The present invention is based on the following general formula () [In formula (), R 1 and R 2 represent the same or different lower alkyl groups, R 3 represents a saturated or unsaturated aliphatic hydrocarbon group substituted with a cyano group or an alkoxycarbonyl group, and represents the position of the carbon atom to which it is attached]
The present invention relates to a method for producing a bromide in which a bromine atom is added to the 3-position carbon and a hydroxyl group or a methoxy group is added to the 2-position carbon of the polyene compound represented by the formula.
臭素化剤として２・４・４・６−テトラブロム
−２・５−シクロヘキサジエン−１−オン（以下
TBCOと略記する）を用いることは公知であり、
これまでに下記反応が試みられている。 2,4,4,6-tetrabromo-2,5-cyclohexadien-1-one (hereinafter referred to as
It is known to use TBCO (abbreviated as TBCO),
The following reactions have been attempted so far.
本発明によれば、一般式HX（式中Ｘは水酸基
またはメトキシ基を表わす）で示される化合物の
存在下、TBCOを前記式（）で示されるポリエ
ン化合物に反応させる場合は、意外にも、２・３
−位の不飽和結合に対して３−位に臭素原子、２
−位にＸがそれぞれ選択的に付加した次式（）
で示される臭素化ポリエン化合物が得られること
が見出された。 According to the present invention, when TBCO is reacted with the polyene compound represented by the formula () in the presence of a compound represented by the general formula HX (wherein X represents a hydroxyl group or a methoxy group), surprisingly, 2・3
Bromine atom at the 3-position relative to the unsaturated bond at the -position, 2
The following formula () with X selectively added to each position:
It has been found that a brominated polyene compound can be obtained.
本発明で用いる式（）のポリエン化合物にお
いて、R1およびR2は同一または異なる低級アル
キル基であり、たとえばメチル、エチル、プロピ
ル、イソプロピル、ｎ−ブチル、イソブチル、ｔ
−ブチル、ｎ−アミル、イソアミル等の炭素数１
〜５のアルキル基を言及しうる。R3はシアノ基
またはアルコキシカルボニル基によつて置換され
ている飽和または不飽和の脂肪族炭化水素基を表
わし、R3中の炭素の総数は１〜30であるのが好
ましい。工業的に特別な有用性が期待できるとい
う意味で、R3はシアノ基またはアルコキシカル
ボニル基によつて置換されているテルペン炭化水
素基であるのが最も望ましい。したがつて本発明
において式（）のポリエン化合物の代表的な例
はゲラニルシアニド、フアルネシルシアニド、ゲ
ラニルゲラニルシアニド、フアルネシル酸メチ
ル、ゲラニルゲラン酸メチル、ゲラニル酢酸メチ
ル、フアルネシル酢酸メチル、ゲラニルゲラニル
酢酸メチル、７−エチル−３・11−ジメチル−
２・６・10−トリデカトリエン酸メチルである。
なおポリエン化合物が左右対象構造を有するとき
は、２・３−位に相当する他端の位置にもＸと臭
素を付加することができる。 In the polyene compound of formula () used in the present invention, R 1 and R 2 are the same or different lower alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t
-1 carbon number such as butyl, n-amyl, isoamyl, etc.
~5 alkyl groups may be mentioned. R 3 represents a saturated or unsaturated aliphatic hydrocarbon group substituted by a cyano group or an alkoxycarbonyl group, and the total number of carbon atoms in R 3 is preferably 1 to 30. Most preferably, R 3 is a terpene hydrocarbon group substituted with a cyano group or an alkoxycarbonyl group in the sense that it can be expected to have special industrial utility. Therefore, in the present invention, typical examples of the polyene compound of formula () are geranyl cyanide, pharnesyl cyanide, geranylgeranyl cyanide, methyl pharnesylate, methyl geranylgeranate, methyl geranyl acetate, methyl pharnesyl acetate, and methyl geranylgeranyl acetate. , 7-ethyl-3,11-dimethyl-
It is methyl 2,6,10-tridecatrienoate.
Note that when the polyene compound has a bilaterally symmetrical structure, X and bromine can also be added to the positions at the other end corresponding to the 2- and 3-positions.
TBCOとの相互作用により式（）のポリエン
化合物の２−位にＸを付加させる一般式HXで示
される化合物は、水またはメタノールであり、こ
れらはポリエン化合物に対して等モル以上の量で
用いられる。一般式HXで示される化合物は大過
剰に用いて溶媒としての機能を兼ねさせることも
可能である。 The compound represented by the general formula HX that adds X to the 2-position of the polyene compound of formula () by interaction with TBCO is water or methanol, and these are used in an amount equal to or more than equimolar to the polyene compound. It will be done. The compound represented by the general formula HX can also be used in large excess to function as a solvent.
本発明においてTBCOの使用量が過少の場合は
転化率が低下し、一方過多の場合は反応の選択性
が低下する。したがつてTBCOはHXで示される
化合物と異なり、その使用量を比較的厳密に調整
する必要があるが、一般にポリエン化合物１モル
あたり約１〜２モルの範囲で用いると最良の結果
が得られる。 In the present invention, if the amount of TBCO used is too little, the conversion rate will decrease, while if it is too much, the selectivity of the reaction will decrease. Therefore, unlike the compound represented by HX, the amount of TBCO used must be controlled relatively strictly, but in general, the best results are obtained when used in a range of about 1 to 2 moles per mole of the polyene compound. .
本発明による反応は、溶媒による希釈下で実施
するのが望ましい。溶媒としてはたとえば塩化メ
チレン、クロロホルム、四塩化炭素等の塩素化炭
化水素；ジエチルエーテル、テトラヒドロフラ
ン、ジオキサン、１・２−ジメトキシエタン等の
エーテル類；アセトニトリル、プロピオニトリル
等の飽和ニトリル；酢酸メチル、酢酸エチル等の
飽和脂肪酸エステル；ニトロメタンで代表される
ニトロアルカンなどを用いることができる。反応
は約−100℃から約50℃までの広い温度範囲で行
なうことができるが、−30℃〜＋30℃がより好ま
しい。 The reaction according to the invention is preferably carried out under dilution with a solvent. Examples of solvents include chlorinated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; saturated nitrites such as acetonitrile and propionitrile; methyl acetate; Saturated fatty acid esters such as ethyl acetate; nitroalkanes represented by nitromethane, etc. can be used. The reaction can be carried out over a wide temperature range from about -100°C to about 50°C, with -30°C to +30°C being more preferred.
本発明により得られる臭素化ポリエン化合物
は、農薬、殺虫剤として、あるいは農薬、殺虫
剤、香料、医薬の製造中間体として有用であり、
たとえば７−エチル−３・11−ジメチル−２・
６・10−トリデカトリエン酸メチルを本発明の方
法によりブロムヒドリンとし、さらに脱臭化水素
することによつてカイコの幼若ホルモンを合成す
ることができる。 The brominated polyene compound obtained by the present invention is useful as an agricultural chemical, an insecticide, or as an intermediate for the production of agricultural chemicals, insecticides, fragrances, and medicines,
For example, 7-ethyl-3.11-dimethyl-2.
Bombyx mori juvenile hormone can be synthesized by converting methyl 6,10-tridecatrienoate into bromohydrin by the method of the present invention and further dehydrobrominating it.
次に実施例により本発明を具体的に説明する。 Next, the present invention will be specifically explained with reference to Examples.
実施例 １
フアルネシル酸メチル519mgを１・２−ジメト
キシエタン20mlおよび塩化メチレン１mlの混合溶
媒中に希釈し、蒸留水２mlとTBCO851mgを加
え、室温で４時間撹拌した。反応混合物より溶媒
を留去し、残留物をエーテルで希釈し、飽和炭酸
ナトリウム水溶液で処理した。エーテル層よりエ
ーテルを留去後、残留物を高速液体クロマトグラ
フイーで分析した結果、フアルネシル酸メチルの
転化率は100％であり、10−ブロム−11−ヒドロ
キシ−３・７・11−トリメチル−２・６−ドデカ
ジエン酸メチルへの選択率は73％であることが判
明した。この残留物をシリカゲルカラムクロマト
グラフイーにより分離精製して、収率69％で10−
ブロム−11−ヒドロキシ−３・７・11−トリメチ
ル−２・６−ドデカジエン酸メチルを得た。この
ものは室温で無色油状物であり、下記のスペクト
ルデータを与えた。Example 1 519 mg of methyl phalanesylate was diluted in a mixed solvent of 20 ml of 1,2-dimethoxyethane and 1 ml of methylene chloride, 2 ml of distilled water and 851 mg of TBCO were added, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off from the reaction mixture, and the residue was diluted with ether and treated with saturated aqueous sodium carbonate solution. After distilling off the ether from the ether layer, the residue was analyzed by high performance liquid chromatography. As a result, the conversion rate of methyl pharnesylate was 100%, and 10-bromo-11-hydroxy-3,7,11-trimethyl- The selectivity to methyl 2,6-dodecadienoate was found to be 73%. This residue was separated and purified by silica gel column chromatography, and the yield was 69%.
Methyl bromo-11-hydroxy-3,7,11-trimethyl-2,6-dodecadienoate was obtained. This was a colorless oil at room temperature and gave the following spectral data.
NMR：δＴＭＳ ＣＣｌ４1.28（6H、ｓ）、1.59（3H、ｓ
）、
1.8〜2.6（11H）、2.65（1H、ｓ）、3.62（3H、
ｓ）、3.80（1H、dd、Ｊ＝３および10Hz）、
5.13（1H、ｍ）、5.59（1H）ppm
IR：νOH＝3480cm-1、νC=O＝1710cm-1
実施例 ２
ゲラニルシアニド312mgをメタノール４mlおよ
び塩化メチレン４mlの混合溶媒中に希釈し、
TBCO786mgを加え室温で１時間撹拌した。反応
混合物より溶媒を留去し、残留物をエーテルで希
釈し、２規定苛性ソーダ水溶液で処理した。エー
テル層よりエーテルを留去後、残留物を高速液体
クロマトグラフイーで分析した結果、ゲラニルシ
アニドの転化率は100％であり、６−ブロム−７
−メトキシ−３・７−ジメチル−２−オクテニル
シアニドへの選択率は92％であることが判明し
た。この残留物をシリカゲルカラムクロマトグラ
フイーにより分離精製して、収率88％で６−ブロ
ム−７−メトキシ−３・７−ジメチル−２−オク
テニルシアニドを得た。このものは室温で無色油
状物であり、下記のスペクトルデータを与えた。NMR: δ TMS CCl4 1.28 (6H, s), 1.59 (3H, s
),
1.8-2.6 (11H), 2.65 (1H, s), 3.62 (3H,
s), 3.80 (1H, dd, J=3 and 10Hz),
5.13 (1H, m), 5.59 (1H) ppm IR: ν OH = 3480cm -1 , ν C=O = 1710cm -1 Example 2 312 mg of geranyl cyanide was diluted in a mixed solvent of 4 ml of methanol and 4 ml of methylene chloride,
786 mg of TBCO was added and stirred at room temperature for 1 hour. The solvent was distilled off from the reaction mixture, and the residue was diluted with ether and treated with a 2N aqueous sodium hydroxide solution. After distilling off the ether from the ether layer, the residue was analyzed by high performance liquid chromatography. As a result, the conversion rate of geranyl cyanide was 100%, and 6-bromo-7
The selectivity to -methoxy-3,7-dimethyl-2-octenyl cyanide was found to be 92%. This residue was separated and purified by silica gel column chromatography to obtain 6-bromo-7-methoxy-3,7-dimethyl-2-octenyl cyanide in a yield of 88%. This was a colorless oil at room temperature and gave the following spectral data.
NMR：δＴＭＳ ＣＣｌ４1.24（3H、ｓ）、1.30（3H、ｓ
）、
1.70（3H、ｓ）、3.02（2H、ｄ、Ｊ＝７Hz）、
3.17（3H、ｓ）、3.83（1H、dd、Ｊ＝２および
10.5Hz）、5.27（1H、ｔ、Ｊ＝７Hz）ppm
IR：νC≡N＝2250cm-1
実施例 11
７−エチル−３・11−ジメチル−２・６・10−
トリデカトリエン酸メチル263mgを１・２−ジメ
トキシエタン10mlおよび塩化メチレン１mlの混合
溶媒中に希釈し、蒸留水３mlおよびTBCO448mg
を加え、室温で10時間撹拌した。反応混合物より
溶媒を留去したのち残留物をエーテルで希釈し、
飽和炭酸ソーダ水溶液で処理した。エーテル層よ
り溶媒を留去したのち、残留物を高速液体クロマ
トグラフイーで分析した結果、７−エチル−３・
11−ジメチル−２・６・10−トリデカトリエン酸
メチルの転化率は100％であり、10−ブロム−７
−エチル−11−ヒドロキシ−３・11−ジメチル−
２・６−トリデカジエン酸メチルへの選択率は77
％であることが判明した。この残留物をシリカゲ
ルカラムクロマトグラフイーで分離精製して、収
率72％で10−ブロム−７−エチル−11−ヒドロキ
シ−３・11−ジメチル−２・６−トリデカジエン
酸メチル〔J.Am.Chem.Soc.、90、5618
（1968）〕を得た。NMR: δ TMS CCl4 1.24 (3H, s), 1.30 (3H, s
),
1.70 (3H, s), 3.02 (2H, d, J=7Hz),
3.17 (3H, s), 3.83 (1H, dd, J=2 and
10.5Hz), 5.27 (1H, t, J = 7Hz) ppm IR: ν C ≡ N = 2250cm -1 Example 11 7-ethyl-3,11-dimethyl-2,6,10-
Dilute 263 mg of methyl tridecatrienate in a mixed solvent of 10 ml of 1,2-dimethoxyethane and 1 ml of methylene chloride, add 3 ml of distilled water and 448 mg of TBCO.
was added and stirred at room temperature for 10 hours. After distilling off the solvent from the reaction mixture, the residue was diluted with ether,
Treated with saturated aqueous sodium carbonate solution. After distilling off the solvent from the ether layer, the residue was analyzed by high performance liquid chromatography, and it was found that 7-ethyl-3.
The conversion rate of methyl 11-dimethyl-2,6,10-tridecatrienoate was 100%, and 10-bromo-7
-ethyl-11-hydroxy-3,11-dimethyl-
Selectivity to methyl 2,6-tridecadienoate is 77
It was found that %. This residue was separated and purified by silica gel column chromatography to obtain methyl 10-bromo-7-ethyl-11-hydroxy-3,11-dimethyl-2,6-tridecadienoate [J.Am. Chem.Soc., 90 , 5618
(1968)].
このものの構造は、メタノール中ナトリウムメ
トキサイドで脱臭化水素してエポキサイド体
とし、該エポキサイド体のNMR及びIRスペクト
ルが文献値〔Angew.Chem.Intern.Ed.Engl.６、
179（1967）〕と一致したことにより確認した。 The structure of this product was obtained by dehydrogenating it with sodium methoxide in methanol. The NMR and IR spectra of the epoxide are the literature values [Angew.Chem.Intern.Ed.Engl. 6 ,
179 (1967)].
Claims (1)
アルキル基を表わし、R3はシアノ基またはアル
コキシカルボニル基によつて置換されている飽和
または不飽和の脂肪族炭化水素基を表わす〕で示
されるポリエン化合物に、一般式HX（式中Ｘは
水酸基またはメトキシ基を表わす）で示される化
合物の存在下、２・４・４・６−テトラブロム−
２・５−シクロヘキサジエン−１−オンを反応さ
せ、一般式（） 〔式（）中R1、R2、R3およびＸは前記意味のと
おりである〕で示される生成物を得ることを特徴
とする臭素化ポリエン化合物の製造方法。[Claims] 1 General formula () [In formula (), R 1 and R 2 represent the same or different lower alkyl groups, and R 3 represents a saturated or unsaturated aliphatic hydrocarbon group substituted by a cyano group or an alkoxycarbonyl group] In the presence of a compound represented by the general formula HX (wherein X represents a hydroxyl group or a methoxy group), 2,4,4,6-tetrabromo-
2,5-cyclohexadien-1-one is reacted to form the general formula () A method for producing a brominated polyene compound, which comprises obtaining a product represented by the formula (in formula (), R 1 , R 2 , R 3 and X are as defined above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6076777A JPS53147006A (en) | 1977-05-24 | 1977-05-24 | Preparation of brominated polyene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6076777A JPS53147006A (en) | 1977-05-24 | 1977-05-24 | Preparation of brominated polyene compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53147006A JPS53147006A (en) | 1978-12-21 |
| JPS6210210B2 true JPS6210210B2 (en) | 1987-03-05 |
Family
ID=13151747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6076777A Granted JPS53147006A (en) | 1977-05-24 | 1977-05-24 | Preparation of brominated polyene compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53147006A (en) |
-
1977
- 1977-05-24 JP JP6076777A patent/JPS53147006A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN=1972 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53147006A (en) | 1978-12-21 |
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